Triazinyl- and pyrimidinyl anthraquinone dyestuffs



United States Patent US. Cl. 260--239.75 3 Claims ABSTRACT OF THE DISCLOSURE The invention provides new reactive water-soluble anthraquinone dyestufis of the formula:

(I) NHz SOaH wherein B represents a phenylene nucleus which may be substituted, R R and R each independently represents H or an alkyl group having 1 to 4 carbon atoms; R represents a divalent aliphatic or carbocyclic radical; X represents N, CC1 or C-CN; W represents C1 or Br; A represents a benzene or naphthalene radical, which may be substituted; Y represents CO or $0 Z represents an alkyl radical having 2 or more carbon atoms and substituted in fi-position to the NH group by C1 or O-SO H; and n represents 1 or 2.

This invention relates to new water-soluble reactive anthraquinone dyestutts, to the methods of preparation thereof and to the use of such dyestuffs for colouring textile materials.

It is known to use dyestuflis containing s-triazine and pyrimidine groups containing reactive halogen atoms for the purpose of colouring fibres containing hydroxyl groups, especially cellulose materials such as cotton and viscose rayon.

These dyestufi's readily fix on such materials with good fastness to wet processing, since the halogen atom is able to react with hydroxyl groups of the cellulose molecule in the presence of acid-binding agents, especially at elevated temperatures. For this purpose, the dyestuffs are applied from aqueous solutions or aqueous printing pastes and, owing to a side-reaction in which the halogen atom reacts with water instead of the cellulose molecule, a considerable portion of the dyestulf does not fix on the fibre.

Consequently an excess of dyestufi must be used and the dyeings or prints must be thoroughly washed with boiling soap solutions to remove the unfixed dyestuif. The wastage of dyestuft and extra processing make the dyeing or printing process more expensive especially when deep shades are required.

The present invention is concerned with the production of water-soluble halogeno-s-triazine and pyrimidine reactive dyestufrs of particular value in textile printing which have a remarkably high fixation on the fibre and for which washing-01f treatments can be reduced considerably.

According to the invention there are provided reactive water-soluble anthraquinone dyestufis of the formula:

wherein B, R, R and R have the meanings stated above,

wherein B represents a phenylene nucleus which may be substiand wlth one mole of an li of the formula R R and R each independently represents H or an alkyl I A L group having 1 to 4 carbon atoms, 5 Rs (5 R represents a divalent aliphatic or carbocyclic radical, h ein A, R Y, Z and n have the meanings stated X represents N, C-Cl or C-CN, above.

W represents C1 or Br, The compounds of Formula 3 which may be used are A represents a benzene 01' napht e rad c Which m y cyanuric chloride, cyanuric bromide, 2:4:5 :-6-tetrachlorobe substituted, 10 or tetrabromo-pyrimidine and 2:4:6-trichloroor tribro- Y represents CO or 50;, mo-S-cyanopyrimidine.

Z represents an alkyl radical having 2 or more carbon A examples of a i f Formula 5, there may be atoms and substituted in fl-position to the NH group by mentioned 3,5-bis-(fl-sulphatoethylsulphamyl) aniline, 3,5- C1 or O-SO H, and bis-(B-sulphatopropylsulphamyl)aniline, 3,5-bis-(f3-chloron represents 1 or 2. ethylsulphamyl)aniline, 3,5 bis (B-chloropropylsulphamyl)aniline, 3,5 bis (,B-sulphatopropylsulphamyl)- t As examples of subst1tuents WlllCl'l may be presen lIl 4 methyl aniline and (fl p p py y the hen lene nucleus represented by B, there may be meniioned methyl, chlorine and sulphonic acid. The sulfi-sulphatopropylsulphamyl)311111116- phonyl group is preferably attached in para or, more es- 2O anthraqmllone compounds of fg c l 4 l f peciany, in meta position to the NH group. venien tly be obtained by the process descri e and c alme As examples of divalent aliphatic radicals represented UI11ted.Klngd0m N0 1,027,261, that is to say,

by R, there may be mentioned alkylene radicals having 2 by contact1ng together 1n an aqueous medium, an anthrato 6 carbon atoms, for example, ethylene, propylene, qumone compound of the formula:

hexamethylene, and alkylene ether radicals, for example H:

O N the -c H,o-c H,- radical. As examples of carboxylic radicals represented by R, SO3H there may be mentioned cycloaliphatic radicals, for example, cyclohexylene, but more especially aromatic carbocyclic radicals, for example benzene, naphthalene, di-

phenyl, diphenylmethane and diphenyloxide radicals, 0 NH-BS2C1 (6) which may be substituted for example, by methyl, chlowhere B has the meaning stated above, and a diamine of rine or sulphonic acid. the formula:

As examples of substituents which may be present in the benzene or naphthalene radical represented by A, R 2

there may be mentioned methyl, chlorine and methoxy.

A preferred class of the new anthraquinone dyestuffs are wherein R, R and R have the meanings stated above.

those represented by the formula: As examples of such anthraquinone compounds, there may i r A sour 11 I I r v osoin 6 NH.C5H4.SOzNH.R4NH-C\ C-NH.CHa(SOzNHCHzHKGHQmHh.

where be mentioned the products obtained by the method described and claimed in United Kingdom Pat. No. 952,497, ggxigg f Sulphophenylene ethylene or that is to say, by heating anthraquinone compounds of the formula:

m is 0 or 1.

0 N According to a further feature of the invention there H is provided a process for manufacture of the new anthra- SOBH quinone dyestuffs which comprises reacting a heterocyclic compound of the formula:

1| I o NHBSO3H I I, in which the ring B can be further substituted, with chloro sulphonic acid either alone or preferably in the presence of I an inorganic halide such as thionyl chloride, phosphorous W (3) trichloride or phosphorous oxychloride.

As examples of amines of Formula 7 there may be mentioned ethylene and proylene diamines and the N-methyl or N,N'-dimethyl derivatives of these, 0-, mor p-phenylene diamines and their nuclearly-substituted derivatives,

wherein X and W have the meanings stated above, in either order, with one mole of an anthraquinone compound of the formula:

N H: e.g. halogenomethyl-, acetylamino-, carboxyor sulpho- 7 O phenylene diamines, their N-methyl or N,N'-dimethyl de- SOaI-I rivatives; also naphthylene diamines and sulphonaphthylene diamines, benzidine, mono or disulpho-benzidines and Y R! R: other nuclearly-substituted benzidines such as 3,3'-dimethoxy benzidine and o-tolidine; diaminodiphenylmeth- O NH B SOZNR NH (4) ane, diaminodiphenyloxide and their sulphonic acids.

The above process can conveniently be carried out by suspending or dissolving the heterocyclic compound in water or in a mixture of water with a water-miscible organic solvent, adding one of the other two reagents, or a solution thereof in water or in a water-miscible organic solvent, stirring the mixture at a suitable temperature until one chlorine or bromine atom on the heterocyclic compound has been reacted, or substantially so, then adding the third reactant and stirring at a suitable temperature to effect reaction of the second chlorine or bromine atom. In general, a temperature of to C. is suitable for the first step and a temperature of 30 to 50 C. is suitable for the second step. The reaction is preferably carried out in the presence of an acid-binding agent, added at such a rate as to maintain the pH of the reaction mixture between the limits of 4 and 9.

The new dyestuffs can be isolated by any of the usual means used in connection with water-soluble reactive dyestuffs, preferably by the addition of sodium chloride, and filtering off the precipitated dyestuff and drying.

The new dyestuffs can be used for dyeing or printing a wide variety of textile materials. They are particularly valuable for use as reactive dyes for the textile printing of cellulose with which they are capable, in the presence of acid-binding agents, of reacting with a high degree of efiiciency and because of the bright reddish-blue shades provided.

The invention is illustrated but not limited by the following examples in which parts are by weight.

EXAMPLE 1 A solution of 6.8-8 parts of disodium salt of 1-amino-4- [3-N-(4" aminophenyl)sulphamylanilino]anthraquinone-2:3"-disulphonic acid in 120 parts of water is added during 20 minutes to a stirred suspension of 2.1 parts of cyanuric chloride in 12 parts of acetone and 80 parts of water at 05 C. The pH of the mixture is maintained by means of 2 N sodium carbonate at 55.5 and Stirring under these conditions is continued for a further 1 hour. The reaction mixture is filtered, the filtrates are adjusted to pH 6.8 and a neutral solution of 5.6 parts of 3:5-bis- (fi-sulphatopropylsulphamyl)aniline in 120 parts of water is added. The mixture is stirred at 35 -40 C. and at pH 6.7 for 4 hours, then a further 2.25 parts of 3:5-bis- ([3-sulphatopropylsulphamyl)aniline dissolved in 50 parts of water is added and stirring is continued at 43-45 C. and at pH 6.7 for 7 hours. The solution is filtered, sodium chloride (20% w./v.) added and the precipitated dyestufi filtered. The product is purified by redissolving in water and reprecipitating by addition of sodium chloride (25% w./v.) and is finally isolated by filtering, washing with 25% (w./v.) sodium chloride solution and drying in vacuo at room temperature. The product contains one hydrolysable chlorine atom per molecule and when applied to cellulosic fibres in conjunction with an acidbinding agent yields bright reddish-blue shades of excellent fastness to wet treatments and to light.

EXAMPLE 2 If the 3:S-bis-(fi-sulphatopropylsulphamyl)aniline used in Example 1 is replaced by the equivalent amount of 3 :5-bis-(p-sulphatoethylsulphamyl) aniline, a dyestufi' possessing very similar properties is obtained.

EXAMPLE 3 q A printing paste is made by mixing together 6.7 grams of the product of Example 1 (containing 5 grams of the pure dyestuff), 20 grams of urea, 35 parts of 4% aqueous sodium alginate, 1 gram of sodium m-nitrobenzene sulphonate and 1.5 grams of sodium carbonate and sufficient water to give 100 grams total weight. This paste is applied to cotton fabric by a roller and the fabric is then baked at 150 C. and 5 minutes, washed in boiling 0.3% detergent for 5 minutes to remove unfixed dyestuff, rinsed in water and dried.

Examination of the washing liquor shows that 9% of the dyestuff had not fixed. By printing on viscose rayon fabric and steaming for 10 minutes at C., a fixation of 88% of dyestuff is achieved.

EXAMPLE 4.

8.6 parts of the disodium salt of l-amino-4-[3'-N-(4"- aminophenyl) sulphamylanilino]anthraquinone 2:3"-disulphonic acid are condensed with 2.6 parts of cyanuric chloride following the procedure described in Example 1, the reaction mixture is filtered and adjusted to pH 7.0 and a neutral solution of 4.6 parts of 3amino-5-([3- chloroethylsulphamyl) benzoic acid in 35 parts of water is added. The mixture is stirred at 35 C. and pH 6.8 to 7.0 for 2 hours, and then at 40 C. and pH 6.8 to 7.0 for 8 hours. The solution is then filtered and adjusted to pH 7.5, sodium chloride (13% w./v.) added with stirring and the dyestufi thus precipitated in filtered off, washed with 14% (w./v.) sodium chloride solution and finally dried in vacuo at room temperature. The product contains 1.93 hydrolysable chlorine atoms per molecule and molecule and yields bright reddish-blue shades of excellent fastness to Wet treatments and to light when applied to cellulosic fibres as described in Example 3.

EXAMPLE 5 If the 3:5 bis (,8 sulphatopropylsulphamyl)aniline used in Example 1 is replaced by the equivalent amount of 4-(,8 sulphatopropylsulphamyl)aniline, a dyestuf'f possessing similar properties is obtained.

EXAMPLE 6 A solution of 5.16 parts of 1-amino-4-[3'-N-(p-aminoethyl)sulphamylanilino]anthraquinone 2 sulphonic acid and 0.6 part of sodium hydroxide in parts of water and 20 parts of acetone is added during 15 minutes, to a stirred suspension of 3.7 parts of cyanuric chloride in 25 parts of acetone and 75 parts of ice-water, the pH of the mixture being maintained at 8.5-9.0 by the addition, when necessary, of 2 N sodium hydroxide solution and the temperature being maintained at 03 C. The reaction mixture is stirred at pH 8.5-9.0 and at 0- 3 C. for a further one hour after the addition, then filtered, the filtrates adjusted to pH 6.5 and a neutral solution of 8.5 parts of 3:5-bis-(B sulphatopropylsulphamyl) aniline in 200 parts of water added. The mixture is stirred at 50-55 C. and the pH maintained at 6.7i0.1 using 2 N sodium carbonate solution for 24 hours, then cooled and filtered and the filtrates are treated with 24% (w./v.) sodium chloride. The dyestuff so precipitated, is filtered, washed with 24% (w./v.) sodium chloride solution and dried. The product contains approximately one hydrolysable chlorine atom per molecule and yields bright reddish-blue shades of excellent fastness when applied to cellulosic fibres in the presence of an acid binding agent.

A similar but slightly greener shade dyestuff is obtained when the above l-amino 4-[ 3' N (pl-aminoethyl) sulphamylanilino] anthraquinone 2 sulphonic acid is replaced by an equivalent amount of l-amino-4-[4'- N-( -aminopropyl)sulphamylanilino]anthraquinone 2 sulphonic acid.

EXAMPLE 7 A solution of 13.76 parts of the disodium salt of 1- amino 4 [3' N (4"-aminophenyl)sulphamylanilino] anthraquinone 2:3"-disulphonic acid in 240 parts of Water is added during 20 minutes to a stirred suspension of 7.0 parts of cyanuric bromide in 25 parts of acetone and parts of water at 0-5 C. The pH of the mixture is maintained by means of 2 N sodium carbonate at 5- 5.5 and stirring under these conditions is continued for a further 45 minutes. The reaction mixture is filtered, the filtrates are adjusted to pH 6.8 and a neutral solution of 6.1 parts of 4-(,@ sulphatopropylcarbamyl) N methylaniline in 150 parts of water is added. The mixture is stirred at 3540 C. and at pH 6.7 for 3 hours and then at 5055 C. and at pH 6.7 for 2 hours. The solution is treated with 20% (w./v.) sodium chloride, and

stirred for 1 hour. The precipitated dyestuff is filtered, washed with 22% (w./v.) sodium chloride solution and finally dried in vacuo at room temperature. The product contains one hydrolysable bromine atom per molecule and when applied to cellulosic fibres in conjunction with an acid-binding agent yields bright reddish-blue shades of excellent fastness to wet treatments and to light.

EXAMPLE 8 A solution of 13.76 parts of the disodium salt of 1- amino 4 [3 N (4"-aminophenyl)sulphamylanilino] anthraquinone 2:3" disulphonic acid in 240 parts of water is added during 20 minutes to a stirred solution of 4.27 parts of 5-cyano-2:4:6-trichloropyrimidine in 90 parts of dioxan and 50 parts of water at C. The pH of the mixture is maintained by means of 2 N sodium carbonate solution at 5.5-6.5 and stirring under these conditions is continued for a further hour. The reaction mixture is filtered, the filtrates are stirred at pH 6.5 and a neutral solution of 6.2 parts of 4-(p-sulphatoethylcarbamyl)-aniline in 150 of water is added. The mixture is stirred at 5560 C. and at pH 6.5 for 6 hours. The solution is treated with 15% (W./v.) sodium chloride and stirred for 1 hour. The precipitated dyestuff is filtered, Washed with 18% (w./v.) sodium chloride solution and finally dried in vacuo at room temperature. The product contains one hydrolysable chlorine atom per molecule and when applied to cellulosic fibres in conjunction with an acid binding agent yields bright reddish blue shades of excellent fastness to wet treatments and to light.

EXAMPLE 9 By substituting a neutral solution of 13.7 parts of 4,8- bis-(fl-sulphatopropylsulphamyl) 2 naphthylamine in 200 parts of water, for the 6.1 parts of 4(B-sulphatopropylcarbamyl)-N-methylaniline in 150 parts of water used in Example 7, a dyestuff of similar shade and wet fastness properties is obtained.

8 We claim: 1. A reactive water-soluble anthraquinone dyestufi of the formula:

and a naphthalene radical of the formula C H Y represents CO or Z represents an alkylene of 2 or 3 carbon atoms and substituted in ,B-position to the NH group by C1 or OSO H, and

n represents 1 or 2.

2. A dyestuff as claimed in claim 1 wherein the S0 group is attached to B in meta position to the NH group.

3. A dyestuff as claimed in claim 1, represented by the formula:

| NHC HiSOaNHlhNH-C OSOaH o-NucsrmsozNncuzcmormmmz where R represents phenylene, sulphophenylene, ethylene or propylene, and m is 0 or 1.

References Cited UNITED STATES PATENTS 3,070,602 12/1962 Buehler 260-249 3,225,043 12/1965 Heslop 260249 3,254,084 5/1966 Fleischhauer et a1. 260 249 3,271,397

9/1966 Bitterli 260256.5

HENRY R. J ILES, Primary Examiner J. M. FORD, Assistant Examiner US. Cl. X.R. 

